US4479006A - Process for the preparation of 1-carbamoyl-3-(3,5-dichlorophenyl)-hydantoins - Google Patents

Process for the preparation of 1-carbamoyl-3-(3,5-dichlorophenyl)-hydantoins Download PDF

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Publication number
US4479006A
US4479006A US06/554,382 US55438283A US4479006A US 4479006 A US4479006 A US 4479006A US 55438283 A US55438283 A US 55438283A US 4479006 A US4479006 A US 4479006A
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process according
carbon atoms
acid acceptor
radical containing
sub
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Inventor
Georges Gros
Marc Molin
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Bayer CropScience SA
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Rhone Poulenc Agrochimie SA
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Priority claimed from FR8012238A external-priority patent/FR2483414A1/fr
Priority claimed from FR8107962A external-priority patent/FR2504132A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/80—Two oxygen atoms, e.g. hydantoin with hetero atoms or acyl radicals directly attached to ring nitrogen atoms

Definitions

  • the present invention relates to a new process for the manufacture of N-substituted 1-carbamoyl-3-(3,5-dichlorophenyl)-hydantoins and also to a new product, namely 1-chlorocarbonyl-3-(3,5-dichlorophenyl)-hydantoin, which can be used as a new intermediate in the manufacture of these products.
  • Certain N-substituted 1-carbamoyl-3-(3,5-dichlorophenyl)-hydantoins are known as plant-protection products, in particular as fungicides for agriculture. This applies particularly to 1-isopropylcarbamoyl-3-(3,5-dichlorophenyl)-hydantoin, commonly referred to as iprodione, which forms the subject of U.S. Pat. Nos. 3,755,350 and 3,823,240. This compound can be prepared in accordance with various processes.
  • the first step referred to as the phosgenation step, is preferably carried out with an excess of phosgene, relative to stoichiometry, in order to prevent the formation of the symmetrical urea resulting from the condensation of the compound of the formula II with the starting compound.
  • the excess must not be too large, since the unreacted part of the phosgene must be degassed at the end of the reaction.
  • the reaction is carried out with an excess of 5 to 100 mol %.
  • This first step is preferably carried out in the presence of at least a stoichiometric amount of an acid acceptor, which in this case is a hydrochloric acid acceptor.
  • This acceptor can be a strong organic base or an inorganic base.
  • the strong organic base which can be used is a tertiary amine, such as a trialkylamine, e.g. triethylamine, or a pyridine, such as pyridine and dimethylaminopyridine.
  • This organic base is advantageously used in an approximately stoichiometric amount.
  • the inorganic base which can be used is an alkali metal carbonate or an alkali metal hydroxide, preference being given to the carbonate and in particular to disodium carbonate.
  • This inorganic base can be used in a stoichiometric amount, but an excess which can range up to about 150% is preferred.
  • the acid acceptor according to the invention can advantageously be associated with an auxiliary agent.
  • the latter can be either an auxiliary base or a transfer agent.
  • the auxiliary base which is associated in an amount of 1 to 15% and preferably of 5 to 10%, is an organic base of the same type as that defined above, but different from the first. Pyridine, dimethylaminopyridine or triethylamine, in particular, can be used for this purpose.
  • the transfer agent which can be used in association with the acid acceptor preferably when the latter is an inorganic base and in particular an alkali metal carbonate, is either an ammonium or phosphonium derivative or a sequestering agent, each of these types of compound being defined below.
  • R 1 , R 2 , R 3 and R 4 which are identical or different, each represent an alkyl radical containing from 1 to 20 carbon atoms, a cycloalkyl radical containing from 3 to 6 carbon atoms, an alkenyl radical containing from 2 to 20 carbon atoms or an optionally substituted phenylalkyl radical in which the alkyl part contains from 1 to 6 carbon atoms
  • X represents a chlorine, bromine or fluorine atom or an SO 4 , SO 4 H, PO 4 H 2 or hydroxyl radical, an alkoxysulphonyloxy radical containing from 1 to 4 carbon atoms (such as methoxysulphonyloxy or ethoxysulphonyloxy), an alkanesulphonyloxy radical containing from 1 to 4 carbon atoms (such as methanesulphonyloxy or
  • Adogen 464 a mixture of methyltrialkylammonium chlorides in which the alkyl parts contain from 8 to 10 carbon atoms, and
  • Cemulcat K 012 a mixture of dihydroxyethyldialkylammonium chlorides in which the alkyl parts contain from 16 to 18 carbon atoms.
  • the catalysts which are preferably used are ammonium derivatives of the formula:
  • R 5 represents an alkyl radical containing from 1 to 4 carbon atoms, such as ethyltributylammonium chloride, methyltributylammonium chloride, tetrabutylammonium chloride or tetrabutylammonium bisulphate.
  • the phosphonium derivatives which can be used according to the present invention preferably correspond to the formula: ##STR6## in which: R' 1 , R' 2 , R' 3 and R' 4 , which are identical or different, each represent an alkyl radical containing from 2 to 8 carbon atoms and Y represents a chlorine or bromine atom.
  • the amount of these derivatives can vary within very wide limits ranging from 0.01 mol to 1 mol per equivalent of basic agent used. In practice, for economic reasons, from 0.5 to 5 mol % of phosphonium derivative is used per mol of main reactant.
  • alkali metal carbonates can also be used advantageously in association with a sequestering agent, which is in itself known, of the formula:
  • n is an integer which is greater than or equal to 0 and less than or equal to about 10 (0 ⁇ n ⁇ 10)
  • R 1 , R 2 , R 3 and R 4 which are identical or different, represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms
  • R 5 represents an alkyl or cycloalkyl radical having from 1 to 12 carbon atoms, a phenyl radical or a radical --C m H 2m -- ⁇ or C m H 2m+1 -- ⁇ --, in which m is between 1 and 12.
  • R 1 , R 2 , R 3 and R 4 represent a hydrogen atom or a methyl radical
  • R 5 having the above meaning and preferably being an alkyl radical having 1 to 4 carbon atoms
  • n having the above meaning and preferably being at least zero and at most 3.
  • the amount of these derivatives is such that their molar proportion, relative to the reactant, is between about 0.5 and 15% and preferably between 1 and 10%.
  • the phosgenation is carried out in an organic solvent which is inert under the reaction conditions.
  • solvents having a relatively high b.p. in order to permit easy degassing of the excess phosgene, in particular aromatic solvents such as toluene or xylene, chlorinated aromatic solvents, such as chlorobenzene, aliphatic solvents, such as dodecane, or chlorinated aliphatic solvents, such as dichloroethane or trichloroethane.
  • the phosgenation can be carried out at a temperature between 0° C. and the b.p. of the reaction medium. However, as the reaction is rather slow by nature, it is advantageous to accelerate it by heating to a temperature between 60° and 130° C. and preferably to the reflux temperature. If the reaction is carried out at elevated temperature, it is advantageously carried out in an autoclave, at pressures which can range up to 5 bars (absolute pressure).
  • the solvent, the phosgene, preferably liquid phosgene, and the starting hydantoin are introduced into the reactor. Since the hydantoin is sparingly soluble in the medium, a suspension is obtained; this is heated and the acid acceptor is added thereto, if appropriate, in order to accelerate the reaction. Heating must be maintained for a sufficiently long time to complete the conversion. It has been found that heating times of 1 to 5 hours are suitable.
  • the first consists in isolating the intermediate chlorocarbonyl, the characteristics of which are given in an example below. It is found that the yield is virtually quantitative.
  • the organic solution of this intermediate can subsequently be used as such in the second stage, referred to as the condensation stage.
  • the medium must be cooled and the excess phosgene must be degassed before starting the second step.
  • the second step is much more rapid than the first and is carried out at a temperature ranging from 0° to 130° C., preferably from 20° to 80° C.
  • Infra-red spectrographic analysis shows the existence of the bands at 1,830-1,820, 1,760 and 1,720 cm -1 which are characteristic of carbonyl groups, corresponding to 1-chlorocarbonyl-3-(3,5-dichlorophenyl)-hydantoin.
  • Example 2 The procedure of Example 1 is followed, the isopropylamine being replaced in the second step by an equivalent amount of ethylamine, n-propylamine, aniline and dimethylamine, respectively.
  • the yields and m.p. of the resulting products are indicated in the following table:
  • variable conditions of the phosgenation and also the yields of intermediate chlorocarbonyl and of 1-isopropyl-3-(3,5-dichlorophenyl)-hydantoin, are recorded in the following table:
  • reaction mixture is subsequently heated at 80° C. for 1 hour 30 minutes and then at 105° C. for the same time.
  • the inorganic substances are filtered off hot (110° C.) and the cake is washed with hot chlorobenzene (130° C.) (2 ⁇ 50 ml). This gives a suspension of 1-chlorocarbonyl-3-(3,5-dichlorophenyl)-hydantoin with a yield of this compound of 94%.
  • Phosgene (4 mols) is then run in and the reaction mixture is heated at 80° C. for 1 hour 30 minutes and then at 105° C. for 1 hour 30 minutes. The total amount of the suspended inorganic substances is filtered off hot (about 110° C.) and the cake is washed with chlorobenzene (2 ⁇ 50 ml) at 130° C.
  • Example 1 This is carried out by following the procedure of Example 1 (second step).
  • the resulting product is isolated by evaporating off the solvent after acid and neutral washing of the chlorobenzene solution.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Indole Compounds (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
US06/554,382 1980-05-29 1983-11-22 Process for the preparation of 1-carbamoyl-3-(3,5-dichlorophenyl)-hydantoins Expired - Fee Related US4479006A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR8012238A FR2483414A1 (fr) 1980-05-29 1980-05-29 Procede de preparation de carbamoyl-1(dichloro-3,5-phenyl)-3-hydantoines et chlorocarbonyl-1(dichloro-3,5-phenyl)-3-hydantoine intermediaire utilisable pour ce procede
FR8012238 1980-05-29
FR8107962A FR2504132A2 (fr) 1981-04-17 1981-04-17 Procede de preparation de carbamoyl-1 (dichloro-3,5-phenyl)-3 hydantoines
FR8107962 1981-04-17

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US06260175 Continuation 1981-05-04

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US (1) US4479006A (enrdf_load_stackoverflow)
EP (1) EP0041465B1 (enrdf_load_stackoverflow)
JP (2) JPS5724367A (enrdf_load_stackoverflow)
AT (1) ATE8625T1 (enrdf_load_stackoverflow)
BR (1) BR8103341A (enrdf_load_stackoverflow)
CA (1) CA1164466A (enrdf_load_stackoverflow)
DD (1) DD159173A5 (enrdf_load_stackoverflow)
DE (1) DE3165038D1 (enrdf_load_stackoverflow)
DK (2) DK231981A (enrdf_load_stackoverflow)
ES (1) ES8207154A1 (enrdf_load_stackoverflow)
HU (1) HU190367B (enrdf_load_stackoverflow)
IE (1) IE51269B1 (enrdf_load_stackoverflow)
IL (1) IL62946A (enrdf_load_stackoverflow)
RO (1) RO82169A (enrdf_load_stackoverflow)
YU (1) YU42404B (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105777647A (zh) * 2016-04-06 2016-07-20 江苏快达农化股份有限公司 一种合成1-异丙基甲酰胺-3-(3,5-二氯苯基)乙内酰脲的方法
CN106008352A (zh) * 2016-06-08 2016-10-12 中国农业科学院植物保护研究所 一种乙内酰脲衍生物及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6413335A (en) * 1987-07-03 1989-01-18 Sumihiko Matsuda Circular package mailing system and packing box therefor
EP0409215B1 (en) * 1989-07-19 1995-04-26 Otsuka Kagaku Kabushiki Kaisha Process for preparing imidazolidine-2,5-dione derivatives
JPH0430435U (enrdf_load_stackoverflow) * 1990-07-07 1992-03-11
AR102942A1 (es) 2014-12-11 2017-04-05 Bayer Cropscience Ag Derivados de arilsulfuro y arilsulfóxido de cinco miembros c-n-conectados, como plaguicidas

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755350A (en) * 1970-10-06 1973-08-28 Rhone Poulenc Sa Substituted 3-phenyl hydantoins useful as fungicides

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2120222A5 (en) * 1970-10-06 1972-08-18 Rhone Poulenc Sa N-acyl-hydantoin derivs - with fungicidal activity
FR2323688A1 (fr) * 1975-09-11 1977-04-08 Rhone Poulenc Ind Nouveau procede de preparation de carbamoyl-1 (dichloro-3,5 phenyl)-3 hydantoines
DE2550964A1 (de) * 1975-11-13 1977-08-04 Basf Ag Hydantoinderivate

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755350A (en) * 1970-10-06 1973-08-28 Rhone Poulenc Sa Substituted 3-phenyl hydantoins useful as fungicides

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Kusuda et al., Chem. Abst., 1974, vol. 80, No. 3516k and 3519p. *
Shibuya et al., Chem. Abst., 1979, vol. 90, No. 23040k. *
Weber et al., Phase Transfer Catalysis in Organic Synthesis, Springer, Berlin, 1977, pp. 6 & 8. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105777647A (zh) * 2016-04-06 2016-07-20 江苏快达农化股份有限公司 一种合成1-异丙基甲酰胺-3-(3,5-二氯苯基)乙内酰脲的方法
CN105777647B (zh) * 2016-04-06 2018-06-01 江苏快达农化股份有限公司 一种合成1-异丙基氨基甲酰胺-3-(3,5-二氯苯基)乙内酰脲的方法
CN106008352A (zh) * 2016-06-08 2016-10-12 中国农业科学院植物保护研究所 一种乙内酰脲衍生物及其制备方法和应用
CN106008352B (zh) * 2016-06-08 2019-06-21 中国农业科学院植物保护研究所 一种乙内酰脲衍生物及其制备方法和应用

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DK325989A (da) 1989-06-30
EP0041465A1 (fr) 1981-12-09
HU190367B (en) 1986-08-28
RO82169A (ro) 1983-07-07
RO82169B (ro) 1983-06-30
JPH0140029B2 (enrdf_load_stackoverflow) 1989-08-24
DK325989D0 (da) 1989-06-30
DD159173A5 (de) 1983-02-23
IE811182L (en) 1981-11-29
BR8103341A (pt) 1982-02-16
EP0041465B1 (fr) 1984-07-25
ATE8625T1 (de) 1984-08-15
ES502559A0 (es) 1982-04-01
DK231981A (da) 1981-11-30
ES8207154A1 (es) 1982-04-01
JPS6128670B2 (enrdf_load_stackoverflow) 1986-07-01
JPS5724367A (en) 1982-02-08
YU137881A (en) 1984-02-29
IE51269B1 (en) 1986-11-26
CA1164466A (en) 1984-03-27
YU42404B (en) 1988-08-31
IL62946A (en) 1985-03-31
DE3165038D1 (en) 1984-08-30
JPS60237073A (ja) 1985-11-25
IL62946A0 (en) 1981-07-31

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